Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D315/00—Heterocyclic compounds containing rings having one oxygen atom as the only ring hetero atom according to more than one of groups C07D303/00 - C07D313/00
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
  • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
  • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
  • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
  • C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
  • C07C29/177—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with simultaneous reduction of a carboxy group

Definitions

• the invention concerns making butyrolactones, butanediols, and mixtures thereof by hydrogenating a variety of hydrogenatable precursors such as maleic acid, fumaric acid, succinic acid, itaconic acid, or mixtures thereof.
• Butyrolactone is a known compound which is employed in the synthesis of pyrrolidone, glutaric acid, and many other compounds. Improved processes for preparing butyrolactone are of interest to the chemical industry.
• U.S. Patent 4,096,156 discloses a process for the preparation of gamma-butyrolactone by catalytic hydrogenation of maleic acid, maleic acid anhydride, succinic acid, succinic acid anhydride, or fumaric acid, or of a mixture of two or more of these compounds.
• the catalyst contains a mixture of an element of the VIII th subgroup of the periodic system of elements or of one of its compounds with an element of group IB of the periodic system of elements or of one of its compounds.
• U.S. 4,105,674 discloses a process for producing gamma-butyrolactone by hydrogenating a feed compound selected from the group consisting of maleic acid, succinic acid, maleic anhydride, succinic anhydride, and mixtures of any of the foregoing in the vapor phase.
• the reaction is conducted in the presence of a Cu-Pd or Cu-Pt catalyst.
• the present invention provides a process for preparing butyrolactones, butanediols, and mixtures thereof comprising hydrogenating a hydrogenatable precursor in the presence of an aqueous reaction medium and a catalyst comprising palladium or combinations thereof with rhenium and at least one support selected from the oxides of titanium, zirconium, and hafnium.
• the invention a process for making butyrolactones, butanediols, and mixtures thereof by hydrogenating a wide variety of hydrogenatable precursors such as maleic acid, maleic anhydride, succinic acid, dimethyl succinate, butylrolactones, itaconic acid or mixtures thereof.
• hydrogenatable precursors such as maleic acid, maleic anhydride, succinic acid, dimethyl succinate, butylrolactones, itaconic acid or mixtures thereof.
• these precursors can be described as dicarboxylic acids, dicarboxylic acid esters, lactones, or mixtures of said acids, esteres, lactones and/or anhydrides.
• the hydrogenatable precursor is an acid and, most preferably, succinic acid, itaconic acid, maleic acid, or fumaric acid.
• the methods of the invention are characterized in that they can be oriented, as desired, toward high ratios of butyrolactones to butanediol
• the catalyst of this invention comprises palladium or combinations thereof with rhenium and at least one support selected from the oxides of titanium, zirconium, and hafnium.
• the catalyst comprises a combination of palladium and rhenium and the support is titanium oxide, and most preferably, the catalyst comprises from about 1 to about 19 weight percent palladium and from about 4 to about 76 weight percent rhenium.
• the catalyst provides substantially 100% conversion of the precursor, high selectivity to and yield of product, and the advantage of being able to control the product ration of butyrolactone/butanediol by varying the reaction temperature, hydrogen pressure and flow rate of the aqueous reaction medium.
• the process is conducted at a temperature of from about 100°C to about 250°C, and most preferably from about 125°C to about 225°C.
• the process is conducted at a pressure of from about 3.5 MPa (500 psig) to about 27.6 MPa (4000 psig), and most preferably from about 3.5 MPa (500 psig) to about 17.3 MPa (2500 psig).
• the process is conducted in the presence of an aqueous reaction medium which can be water or an aqueous solution containing water soluble substances such as methanol, ethanol, tetrahydrofuran or 1,4-dioxane.
• an aqueous reaction medium which can be water or an aqueous solution containing water soluble substances such as methanol, ethanol, tetrahydrofuran or 1,4-dioxane.
• the aqueous reaction medium is water.
• concentration of precursor is not critical.
• the precursor can be employed in dilute solutions to near the maximum solubility level, typically from about 1 to about 50 weight percent.
• the liquid phase hydrogenation of the invention can be run using conventional apparatus and techniques in a stirred-tank reactor or in a fixed-bed reactor. Hydrogen is fed continuously, generally in considerable stoichiometric excess with no inert diluent gases. Unreacted hydrogen can be returned to the reactor as a recycle stream. The reaction can be run in the batch or continuous mode.
• the catalysts were prepared by adding 20 g of support to a solution containing the desired amount of PdCl2, 3 mL of concentrated hydrochloric acid and 15 mL of distilled water. The resultant slurry was stirred for three hours at ambient temperature and dried at 110° for 18 hours. The resulting supported catalyst was then heated in a furnace for one hour at 150° in an atmosphere of helium (flow rate 100 mL/min), followed by heating at 150° for one hour and 300° for three hours in an atmosphere of helium (flow rate 100 mL/min) and hydrogen (flow rate 100 mL/min). While still maintaining the hydrogen helium atmosphere, the catalyst was cooled to ambient temperature and passivated at ambient temperature with an atmosphere of 1.8% oxygen in nitrogen for 18 hours.
• the resulting reduced catalyst was added to a solution containing the desired amount of ammonium perrhenate and 6 mL of distilled water.
• the resultant slurry was treated as described above.
• the catalyst so prepared were granulated to 16 to 19 mesh (U.S. Standard Sieve Units) and charged into the reactor employed in the Examples and Comparative Experiments. Prior to start of the liquid feed the granulated catalysts were reduced in the reactor for about two hours each at 100°, 150°, and 200° in a stream of hydrogen.
• Example 2 The process described in Example 1 was substantially repeated two times except that the reaction mixture was a solution of 5% succinic acid and 2% dioxane in water and the catalyst was 1.70 g of 1% Pd and 4% Re on carbon. The results are shown in Table 2.
• Example 1 The process described in Example 1 was substantially repeated three times except that the reaction mixture was a solution of 4% itaconic acid and 2% dioxane in water and the catalyst was 4.12 g of 1% Pd and 4% Re on titanium oxide.
• Product leaving the reactor was analyzed by conventional chromatography to determine selectivity to 3- and 4- methyl gamma- butyrolactone (MeGBL(3&4)) and 2-methyl-1,4-butanediol (MeBDO). The results are shown in Table 3.
• Example 1 The process described in Example 1 was substantially repeated four times except that the reaction mixture was a solution of 5% maleic acid and 2% dioxane in water, the pressure was 3.5 MPa (500 psig), and the catalysts were as specified in Table 4.
• the catalysts were 1% Pd and 4% Re; in Example 10, the catalyst was 0.5% Pd and 0.5% Re; and in Example 11, the catalyst was 0.5% Pd.
• Table 4 The results are shown in Table 4.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Catalysts (AREA)
• Furan Compounds (AREA)

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• 1987
  • 1987-01-23 US US07/006,239 patent/US4782167A/en not_active Expired - Lifetime
• 1988
  • 1988-01-22 EP EP88100922A patent/EP0276012B1/fr not_active Expired - Lifetime
  • 1988-01-22 DE DE8888100922T patent/DE3870633D1/de not_active Expired - Lifetime
  • 1988-01-22 JP JP63012430A patent/JP2744428B2/ja not_active Expired - Fee Related

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